Ion exchangeable glass with deep compressive layer and high damage threshold

ABSTRACT

Glasses comprising SiO 2 , Al 2 O 3 , and P 2 O 5  that are capable of chemical strengthened by ion exchange and having high damage resistance. These phosphate-containing glasses have a structure in which silica (SiO 2 ) is replaced by aluminum phosphate (AlPO 4 ) and/or boron phosphate (BPO 4 ).

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No. 15/152,020 filed on May 11, 2016, which is a continuation of U.S. patent application Ser. No. 13/305,271 filed on Nov. 28, 2011, which claims the benefit of priority under 35 U.S.C. § 119 of U.S. Provisional Application Ser. No. 61/417,941, filed on Nov. 30, 2010, the content of which is relied upon and incorporated herein by reference in its entirety.

BACKGROUND

The disclosure relates to glasses that are damage resistant. More particularly, the disclosure relates to damage resistant phosphate-containing glasses. Even more particularly, the disclosure relates to damage resistant phosphate-containing glasses that are strengthened by ion exchange.

In many applications, glasses are chemically strengthened by ion exchange, which forms a compressive surface layer in the glass. This layer is resistant to the propagation of cracks due impact. Further damage resistance may be provided through the inclusion of boron as B₂O₃ in the composition.

SUMMARY

Glasses comprising SiO₂, Al₂O₃, and P₂O₅ that are capable of chemical strengthening by ion exchange and having high damage resistance are provided. These phosphate-containing glasses have a structure in which silica (SiO₂) in the glass is replaced by aluminum phosphate (AlPO₄), which consists of tetrahedrally coordinated aluminum and phosphorus and/or replaced by boron phosphate (BPO₄), which consists of tetrahedrally coordinated boron and phosphorus. The glasses inherently have Vickers crack initiation (i.e., median and/or radial crack initiation) thresholds of at least 500 gf (gram force). When strengthened by ion exchange, the glasses have Vickers damage resistance thresholds of at least about 10 kgf (kilogram force).

Accordingly, one aspect of the disclosure is to provide a glass. The glass comprises SiO₂, Al₂O₃, P₂O₅, and at least one alkali metal oxide (R₂O), wherein 0.75≤[(P₂O₅ (mol %)+R₂O (mol %))/M₂O₃ (mol %)]≤1.3, where M₂O₃=Al₂O₃+B₂O₃.

A second aspect of the disclosure is to provide a glass. The glass comprises SiO₂, Al₂O₃, P₂O₅, and at least one alkali metal oxide (R₂O), wherein 0.75≤[(P₂O₅ (mol %)+R₂O (mol %))/M₂O₃ (mol %)]≤1.3, where M₂O₃=Al₂O₃+B₂O₃, and wherein the glass, when ion exchanged, has a Vickers median/radial crack initiation threshold of at least about 10 kgf.

These and other aspects, advantages, and salient features will become apparent from the following detailed description, the accompanying drawings, and the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic cross-sectional view of a glass sheet strengthened by ion exchange;

FIG. 2 is a plot of compressive stress and depth of layer as functions of AlPO₄ concentration for 0.7 mm thick phosphate-containing glass samples that were ion exchanged in a molten KNO₃ salt bath at 410° C. for 8 hours;

FIG. 3 is a plot of compressive stress and depth of layer as functions of AlPO₄ concentration for 0.7 mm thick phosphate-containing glass samples that were ion exchanged in a molten KNO₃ salt bath at 450° C. for 1 hour;

FIG. 4 is a plot of compressive stress and depth of layer as functions of AlPO₄ concentration for 0.7 mm thick phosphate-containing glass samples that were ion exchanged in a molten KNO₃ salt bath at 450° C. for 30 minutes; and

FIG. 5 is a plot of Vickers crack initiation threshold as a function of AlPO₄ concentration for boron-free phosphate-containing glasses that were ion exchanged in a molten KNO₃ salt bath at 450° C. for 30 minutes.

DETAILED DESCRIPTION

In the following description, like reference characters designate like or corresponding parts throughout the several views shown in the figures. It is also understood that, unless otherwise specified, terms such as “top,” “bottom,” “outward,” “inward,” and the like are words of convenience and are not to be construed as limiting terms. In addition, whenever a group is described as comprising at least one of a group of elements and combinations thereof, it is understood that the group may comprise, consist essentially of, or consist of any number of those elements recited, either individually or in combination with each other. Similarly, whenever a group is described as consisting of at least one of a group of elements or combinations thereof, it is understood that the group may consist of any number of those elements recited, either individually or in combination with each other. Unless otherwise specified, a range of values, when recited, includes both the upper and lower limits of the range. As used herein, the indefinite articles “a,” “an,” and the corresponding definite article “the” mean “at least one” or “one or more,” unless otherwise specified.

As described herein, the Vickers indenter that is used to measure crack initiation is known in the art and described, for example, in pages 130-132 of “Materials Science and Engineering (third edition)” by William D. Callister (John Wiley & Sons, New York, 1994), which are incorporated by reference herein. Unless otherwise specified, the Vickers indentation cracking threshold measurements described herein are performed by applying and then removing an indentation load to the glass surface at 0.2 mm/min. The indentation maximum load is held for 10 seconds. The indentation cracking threshold is defined at the indentation load at which greater than 50% of 10 indents exhibit any number of radial/median cracks emanating from the corners of the indent impression. The maximum load is increased until the threshold is met for a given glass composition. All indentation measurements are performed at room temperature in 50% relative humidity.

As described herein, abraded ring-on-ring failure loads obtained for glass samples was determined by first blasting the surface of the sample to be studied (typical dimensions are 50 mm×50 mm×0.7 mm thick) with 90 grit silicon carbide (SiC) at a pressure of 5 psi for five seconds. Samples are masked so that the abrasion is limited to a 6×mm diameter circle located at the center of the 50 mm×50 mm faces of the sample. Abrasion of the samples was followed by ring-on-ring load-to failure-testing with a 1 inch diameter support ring and a ½ inch diameter loading ring. The sample is placed on the support ring with the abraded side face down, so as to put the abraded region in tension during testing. The load is applied at a rate of 1.2 mm/min. Testing is performed at room temperature in 50% relative humidity. The radius of curvature on the rings is 1/16 inch.

Referring to the drawings in general and to FIG. 1 in particular, it will be understood that the illustrations are for the purpose of describing particular embodiments and are not intended to limit the disclosure or appended claims thereto. The drawings are not necessarily to scale, and certain features and certain views of the drawings may be shown exaggerated in scale or in schematic in the interest of clarity and conciseness.

Glasses designed for use in applications such as in consumer electronics, automotive applications, appliances, architectural components, and other areas where high levels of damage resistance are desirable are frequently strengthened by thermal means (e.g., thermal tempering) or chemical means. Ion exchange is widely used to chemically strengthen glass articles for such applications. In this process, a glass article containing a first metal ion (e.g., alkali cations in Li₂O, Na₂O, etc.) is at least partially immersed in or otherwise contacted with an ion exchange bath or medium containing a second metal ion that is either larger or smaller than the first metal ion that is present in the glass. The first metal ions diffuse from the glass surface into the ion exchange bath/medium while the second metal ions from the ion exchange bath/medium replace the first metal ions in the glass to a depth of layer below the surface of the glass. The substitution of larger ions for smaller ions in the glass creates a compressive stress at the glass surface, whereas substitution of smaller ions for larger ions in the glass typically creates a tensile stress at the surface of the glass. In some embodiments, the first metal ion and second metal ion are monovalent alkali metal ions. However, other monovalent metal ions such as Ag⁺, Tl⁺, Cu⁺, and the like may also be used in the ion exchange process.

A cross-sectional view of a portion (i.e., ends of the glass sheet are not shown) of a glass sheet strengthened by ion exchange is schematically shown in FIG. 1. In the non-limiting example shown in FIG. 1, strengthened glass sheet 100 has a thickness t, central portion 115, and a first surface 110 and second surface 120 that are substantially parallel to each other. Compressive layers 112, 122 extend from first surface 110 and second surface 120, respectively, to depths of layer d₁, d₂ below each surface. Compressive layers 112, 122 are under a compressive stress, while central portion 115 is under a tensile stress, or in tension. The tensile stress in central portion 115 balances the compressive stresses in compressive layers 112, 122, thus maintaining equilibrium within strengthened glass sheet 100. Whereas a glass sheet having compressive layers 112, 122 extending from opposite surfaces 110, 120 is shown in FIG. 1, the glass described herein can have a single surface that is strengthened by ion exchange, rather than multiple strengthened surfaces 110, 120. This can be achieved, for example, by masking one of surfaces 110, 120 during ion exchange process.

In order to increase damage resistance, boron is sometimes added to glasses as B₂O₃. However, the presence of B₂O₃ may impede the strengthening of glasses by ion exchange. It has been discovered that addition of phosphorous to the glass as P₂O₅ improves damage resistance and does not impede ion exchange. The addition of phosphorous to the glass creates a structure in which silica (SiO₂ in the glass) is replaced by aluminum phosphate (AlPO₄), which consists of tetrahedrally coordinated aluminum and phosphorus and/or boron phosphate (BPO₄), which consists of tetrahedrally coordinated boron and phosphorus. As described herein, ion exchangeable phosphate-containing glasses, as well as phosphate-containing glasses that are chemically strengthened by ion exchange and having high damage resistance, are provided. These glasses comprise SiO₂, Al₂O₃, P₂O₅, and at least one alkali metal oxide (R₂O, where R is Li, Na, K, Rb, and/or Cs), wherein 0.75≤[(P₂O₅ (mol %)+R₂O (mol %))/M₂O₃ (mol %)]≤1.3, where M₂O₃=Al₂O₃+B₂O₃. In some embodiments, [(P₂O₅ (mol %)+R₂O (mol %))/M₂O₃ (mol %)]=1. In some embodiments, the glass does not include B₂O₃ and M₂O₃=Al₂O₃. The glass comprises, in some embodiments: about 40 to about 70 mol % SiO₂; 0 to about 28 mol % B₂O₃; about 0 to about 28 mol % Al₂O₃; about 1 to about 14 mol % P₂O₅; and about 12 to about 16 mol % R₂O. In some embodiments, the glass comprises, in some embodiments: about 40 to about 64 mol % SiO₂; 0 to about 8 mol % B₂O₃; about 16 to about 28 mol % Al₂O₃; about 2 to about 12 mol % P₂O₅; and about 12 to about 16 mol % R₂O. The glass may further comprise at least one alkaline earth metal oxide such as, but not limited to, MgO or CaO. Exemplary compositions of the glasses, expressed in mol %, are listed in Table 1. The M₂=O₃ content (where M₂O₃=Al₂O₃+B₂O₃), combined P₂O₅+R₂O concentration, (P₂O₅+R₂O)/M₂O₃ ratio, and (P₂O₅+R₂O)/Al₂O₃ ratio of these compositions are also listed in Table 1.

In one aspect, the phosphate-containing glasses described herein have a structure in which silica (SiO₂) in the glass is replaced by aluminum phosphate (AlPO₄), which consists of tetrahedrally coordinated aluminum and phosphorus. Table 1 lists the equivalent concentrations of AlPO₄ units in the glass for compositions given in the table. In such embodiments, the glass compositions described herein follow the rule that Al₂O₃=P₂O₅+R₂O, where Al₂O₃, P₂O₅, and R₂O are compositions expressed in mol %. When such conditions exist within the glass, aluminum will nominally be in the form of either tetrahedral aluminum. The phosphorus and/or alkalis charge compensate aluminum ions so that they have the equivalent of a 4+ charge.

In another aspect, the phosphate-containing glasses described herein have a structure in which silica (SiO₂) is replaced by boron phosphate (BPO₄) in the glass. In such embodiments, the glass compositions described herein follow the rule that Al₂O₃=R₂O and B₂O₃, =P₂O₅, where Al₂O₃, B₂O₃, P₂O₅, and R₂O are compositions expressed in mol %. When such conditions exist within the glass, boron will nominally be in the form tetrahedral boron phosphate or tetrahedral boron oxide.

In glasses such as those described herein, each alkali metal ion is capable of creating one non-bridging oxygen (NBO). The unit positive charge on an alkali metal ion can be satisfied by an ionic bond to an oxygen in the silicate glass network. This is accomplished by breaking a bridge between adjacent structural units, while donating an oxygen from the R₂O unit. NBOs reduce the connectivity of the glass network. When Al₂O₃ and/or B₂O₃ are added to the glass, the alkali metal ions will charge compensate for the Al³⁺ and/or B³⁺ ions and allow these ions to form tetrahedral structural units. The oxygen supplied by the R₂O units is consumed to form these tetrahedra. Each added aluminum or boron ion will remove one NBO from the glass network. If mol % Al₂O₃+mol % B₂O₃=mol % R₂O, the structure should not contain any NBOs and should be fully linked. Alkalis are preferentially consumed by aluminum over boron. The remaining alkalis convert trigonal boron to tetrahedral boron until [Na₂O (mol %)/B₂O₃ (mol %)]>0.5. Accordingly, the glasses described herein are substantially free of NBOs when the above equation is satisfied. Because AlPO₄ and/or BPO₄ are substituted for silica in the glass, the amount of silica in the glasses described herein is lower than in other ion exchangeable glasses.

The phosphate-containing glasses described herein are inherently resistant to damage; i.e., they are damage-resistant in the absence of any thermal or chemical strengthening such as, for example, ion exchange. The phosphate-containing glasses described herein have Vickers indentation damage (crack initiation load) thresholds of at least about 500 gf (gram force) and, in some embodiments, at least about 1000 gf. Vickers indentation cracking thresholds measured for selected prior to strengthening by ion exchange are listed in Table 1.

In some embodiments, the phosphate-containing glasses described herein have molar volumes of at least about 29 cm³/mol, in other embodiments, at least about 30 cm³/mol, and in still other embodiments at least about 32 cm³/mol. Molar volumes of selected glass compositions are listed in Table 1.

The phosphate-containing glasses described herein are also ion exchangeable to a greater depth of compressive layer (depth of layer d₁, d₂ in FIG. 1) below the surface of the glass than soda lime, alkali aluminosilicate, and alkali aluminoborosilicate glasses. The depth of the compressive layer (112, 122 in FIG. 1) has been shown to be a critical factor in crack resistance of cover glasses for portable electronic devices during system level drop tests. In some embodiments, the phosphate-containing glasses are ion exchangeable to a depth of layer of at least 40 μm and, in other embodiments, to a depth of layer of at least about 60 μm. Compressive stresses and depths of layer obtained by ion exchange in a molten KNO₃ salt bath at 410° C. for 8 hours of 0.7 mm thick phosphate-containing glasses (samples 3, 10-13, and 18-20 in Tables 1-3) described herein are plotted as functions of AlPO₄ concentration in FIG. 2. Each of the samples plotted in FIG. 2 contain no boron and have (P₂O₅+R₂O)/M₂O₃ and (P₂O₅+R₂O)/Al₂O₃ ratios that are equal to 1. The depth of layer of the compressive surface layer is at least 78 μm and the compressive stress is at least 692 MPa, as determined by photoelastic methods known in the art. Compressive stresses and depths of layer obtained by ion exchange in a molten KNO₃ salt bath at 410° C. for 8 hours of phosphate-containing glasses described herein, as well as Vickers indentation crack initiation loads and abraded ring-on-ring failure load for various P₂O₅ containing glasses are listed in Table 2. In one non-limiting example, a depth of compressive layer of 64 μm is achieved when 0.7 mm thick samples of the phosphate-containing glasses described herein are ion-exchanged in a molten KNO₃ salt bath at 410° C. for 10 hours, whereas a depth of compressive layer of 56 μm is achieved when alkali aluminosilicate glass samples that do not comprise P₂O₅ and having the same thickness undergo ion exchange under the same conditions. When ion exchanged in a molten KNO₃ salt bath at 410° C. for 8 hours, 0.7 mm thick samples of the phosphate-containing glasses described herein have a depth of compressive layer of at least about 60 μm and compressive stress of greater than about 600 MPa. In comparison, 0.7 mm thick samples of alkali aluminosilicate glasses that do not comprise P₂O₅ ion exchange to a compressive depth of layer of 50 μm under the same conditions.

In addition, ion exchange proceeds more quickly in the phosphate-containing glasses described herein than in those glasses where the expression 0.75≤R[(P₂O₅ (mol %)+R₂O (mol %))/M₂O₃ (mol %)]≤1.3 is not satisfied. In some embodiments, the phosphate-containing glasses described herein, when ion-exchanged for 2 hours at 410° C. in a molten KNO₃ salt bath, are capable of ion exchange to a depth of layer extending to at least about 30 μm from a surface of the glass. Compressive stresses and depths of layer of phosphate-containing glasses described herein, obtained by ion exchange in a molten KNO₃ salt bath at 410° C. for 2 hours, as well as Vickers indentation crack initiation loads are listed in Table 2.

TABLE 1 Compositions of phosphorus-containing glasses Sample mol % 1 2 3 4 5 6 7 8 9 10 SiO₂ 46 48 50 44 42 49 52 43 40 52 B₂O₃ 4 2 0 6 8 4 4 4 4 0 Al₂O₃ 25 25 25 25 25 23.5 22 26.5 28 24 P₂O₅ 9 9 9 9 9 7.5 6 10.5 12 8 Na₂O 14 14 14 14 14 14 14 14 14 14 K₂O 2 2 2 2 2 2 2 2 2 2 SnO₂ 0 0 0 0 0 0 0 0 0 0 AlPO₄ equivalent 18 18 18 18 18 15 12 21 24 16 BPO₄ equivalent M₂O₃ 29 27 25 31 33 27.5 26 30.5 32 24 P₂O₅ + R₂O 25 25 25 25 25 23.5 22 26.5 28 24 (P₂O₅ + R₂O)/M₂O₃ 0.86 0.93 1.00 0.81 0.76 0.85 0.85 0.87 0.88 1.00 (P₂O₅ + R₂O)/Al₂O₃ 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Molar Volume (cm³/mol) 33.30 32.97 32.73 33.46 33.58 32.46 31.59 33.98 34.76 32.23 Pre-IX Vickers Crack 500- 1000- 1000- 1000- 1000- 1000- 1000- 1000- 1000- 1000- Initiation Load (gf) 1000 2000 2000 2000 2000 2000 2000 2000 2000 2000 Anneal Pt. (° C.) 652 698 739 614 572 661 667 650 645 748 Strain Pt. (° C.) 593 637 675 559 521 602 607 593 589 683 Temperature at Visc = 1187 1232 1276 1142 1097 1206 1226 1167 1147 1289 35 kP (° C.) Temperature Zircon Breakdown (° C.) Liquidus Viscosity (poise) Sample mol % 11 12 13 14 15 16 17 18 19 20 SiO₂ 54 56 58 50 50 50 50 60 62 64 B₂O₃ 0 0 0 0 0 0 0 0 0 0 Al₂O₃ 23 22 21 27 23 25 25 20 19 18 P₂O₅ Na₂O 7 6 5 7 11 9 9 4 3 2 K₂O 14 14 14 14 14 13 15 14 14 14 SnO₂ 2 2 2 2 2 3 1 2 2 2 AlPO₄ equivalent 0 0 0 0 0 0 0 0 0 0 BPO₄ equivalent 14 12 10 14 18 18 8 6 4 M₂O₃ 23 22 21 27 23 25 25 20 19 18 P₂O₅ + R₂O 23 22 21 23 27 25 25 20 19 18 (P₂O₅ + R₂O)/M₂O₃ 1.00 1.00 1.00 0.85 1.17 1.00 1.00 1.00 1.00 1.00 (P₂O₅ + R₂O)/Al₂O₃ 1.00 1.00 1.00 0.85 1.17 1.00 1.00 1.00 1.00 1.00 Molar Volume (cm³/mol) 31.52 31.36 30.7 32.3 33.42 32.91 32.62 30.04 29.38 29.15 Pre-IX Vickers Crack 1000- 1000- 1000- 1000- 1000- 1000- 1000- 1000- 500- 500- Initiation Load (gf) 2000 2000 2000 2000 2000 2000 2000 2000 1000 1000 Anneal Pt. (° C.) 733.3 740 757 794 685 737 741 770 779 789 Strain Pt. (° C.) 669.3 676 690 725 626 672 678 705 712 722 Temperature at Visc = 1303 1316 1317 1312 1241 1278 1275 1338 1359 1377 35 kP (° C.) Temperature Zircon 1135 1130 Breakdown (° C.) Liquidus Viscosity (poise) 1.75E+09 1.18E+14 3.06E+13 6.58E+12 Sample mol % 21 22 23 24 25 26 27 28 29 30 SiO₂ 58 60 62 58 60 62 64 58 60 62 B₂O₃ 4 4 4 5 4 3 2 2 2 2 Al₂O₃ 19 18 16 16 16 16 16 20 19 18 P₂O₅ 3 2 2 5 4 3 2 4 3 2 Na₂O 14 14 14 14 14 14 14 14 14 14 K₂O 2 2 2 2 2 2 2 2 2 2 SnO₂ 0 0 0 0 0 0 0 0 0 0 AlPO₄ equivalent 6 4 8 6 4 BPO₄ equivalent 4 10 8 6 4 M₂O₃ 23 22 20 21 20 19 18 22 21 20 P₂O₅ + R₂O 19 18 18 21 20 19 18 20 19 18 (P₂O₅ + R₂O)/M₂O₃ 0.83 0.82 0.90 1.00 1.00 1.00 1.00 0.91 0.90 0.90 (P₂O₅ + R₂O)/Al₂O₃ 1.00 1.00 1.13 1.31 1.25 1.19 1.13 1.00 1.00 1.00 Molar Volume (cm³/mol) 29.61 29.28 29.26 30.39 30.15 29.79 29.08 30.36 30.49 29.35 Pre-IX Vickers Crack 1000- 1000- 1000- 1000- 1000- 1000- 1000- 1000- 1000- 1000- Initiation Load (gf) 2000 2000 2000 2000 2000 2000 2000 2000 2000 2000 Anneal Pt. (° C.) 669 674 649 602 629 666 699 714 717 723 Strain Pt. (° C.) 606 609 587 545 569 603 633 649 653 656 Temperature at Visc = 1259 1277 1273 1223 1251 1293 1329 1289 1309 1323 35 kP (° C.) Temperature Zircon >1263 1225 1200 1162 Breakdown (° C.) Liquidus Viscosity (poise) 8.04E+08 1.17E+09 9.34E+08 2.89E+09 1.79E+09 6.09E+09 3.98E+11 5.45E+11 Sample mol % 31 32 33 34 35 36 37 38 39 40 SiO₂ 59 61 69 69 62 62 59.9 59.88 60 62 B₂O₃ 1 1 3 2 3 3 4 4 4.5 4.5 Al₂O₃ 20 19 12.5 13.5 15 15 16 18 15.5 13.5 P₂O₅ 4 3 3 2 3 3 4 2 4 4 Na₂O 14 14 12 13 15 14 15.5 15.5 15.5 15.5 K₂O 2 2 0.5 0.5 2 3 0.5 0.5 0.5 0.5 SnO₂ 0 0 0 0 0 0 0.1 0.1 0 0 AlPO₄ equivalent 8 6 4 BPO₄ equivalent 6 4 8 4 8 M₂O₃ 21 20 15.5 15.5 18 18 20 22 20 18 P₂O₅ + R₂O 20 19 15.5 15.5 20 20 20 18 20 20 (P₂O₅ + R₂O)/M₂O₃ 0.95 0.95 1.00 1.00 1.11 1.11 1.00 0.82 1.00 1.11 (P₂O₅ + R₂O)/Al₂O₃ 1.00 1.00 1.24 1.15 1.33 1.33 1.25 1.00 1.29 1.48 Molar Volume (cm³/mol) 30.43 29.99 29.06 28.63 29.33 29.52 29.67 29.15 29.72 29.31 Pre-IX Vickers Crack 1000- 1000- 1000- 1000- 500- 500- 1000- 1000- 1000- 1000- Initiation Load (gf) 2000 2000 2000 2000 1000 1000 2000 2000 2000 2000 Anneal Pt. (° C.) 738 739 656 698 625 639 641 690 616 594 Strain Pt. (° C.) 673 673 589 630 569 581 581 627 561 542 Temperature at Visc = 1314 1327 1346 1362 1245 1260 1242 1264 1223 1188 35 kP (° C.) Temperature Zircon >1255 1225 1110 >1258 Breakdown (° C.) Liquidus Viscosity (poise) 3.48E+12 5.82E+09 3.74E+11 4.91E+09 Sample mol % 41 42 43 44 45 46 47 48 49 50 SiO₂ 62 62 62 58 58 58 58 60 60 60 B₂O₃ 2.5 4.5 4.5 4.5 6.5 4.5 4.5 2.5 4.5 4.5 Al₂O₃ 15.5 15.5 15.5 17.5 15.5 15.5 15.5 17.5 17.5 17.5 P₂O₅ 4 2 4 4 4 6 4 4 2 4 Na₂O 15.5 15.5 13.5 15.5 15.5 15.5 17.5 15.5 15.5 13.5 K₂O 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 SnO₂ 0 0 0 0 0 0 0 0 0 0 AlPO₄ equivalent BPO₄ equivalent M₂O₃ 18 20 20 22 22 20 20 20 22 22 P₂O₅ + R₂O 20 18 18 20 20 22 22 20 18 18 (P₂O₅ + R₂O)/M₂O₃ 1.11 0.90 0.90 0.91 0.91 1.10 1.10 1.00 0.82 0.82 (P₂O₅ + R₂O)/Al₂O₃ 1.29 1.16 1.16 1.14 1.29 1.42 1.42 1.14 1.03 1.03 Molar Volume (cm³/mol) 29.51 28.90 29.92 30.00 29.92 30.5 29.56 29.82 29.21 30.16 Pre-IX Vickers Crack 1000- 1000- 1000- 1000- 1000- 1000- 1000- 500- 500- 1000- Initiation Load (gf) 2000 2000 2000 2000 2000 2000 2000 1000 1000 2000 Anneal Pt. (° C.) 649 633 638 641 588 592 593 679 666 656 Strain Pt. (° C.) 590 576 577 582 539 542 547 616 606 594 Temperature at Visc = 1277 1259 1273 1240 1181.3 1195 1166 1287 1259 1267 35 kP (° C.) Temperature Zircon Breakdown (° C.) Liquidus Viscosity (poise) 1.50E+08 Sample mol % 51 52 53 54 55 56 57 58 59 60 SiO₂ 60 60 60 60 60 60 60 60 60 60 B₂O₃ 6.5 6.5 2.5 2.5 4.5 4.5 4.5 4.5 4.5 4.5 Al₂O₃ 15.5 15.5 15.5 15.5 15.5 15.5 15.4 15.4 15.4 15.4 P₂O₅ 2 4 6 4 6 2 4 4 3.5 4 Na₂O 15.5 13.5 15.5 17.5 13.5 17.5 15.5 16 16.5 15.5 K₂O 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0 0 0.5 SnO₂ 0 0 0 0 0 0 0.1 0.1 0.1 0.1 AlPO₄ equivalent BPO₄ equivalent M₂O₃ 22 22 18 18 20 20 19.9 19.9 19.9 19.9 P₂O₅ + R₂O 18 18 22 22 20 20 20 20 20 20 (P₂O₅ + R₂O)/M₂O₃ 0.82 0.82 1.22 1.22 1.00 1.00 1.01 1.01 1.01 1.01 (P₂O₅ + R₂O)/Al₂O₃ 1.16 1.16 1.42 1.42 1.29 1.29 1.30 1.30 1.30 1.30 Molar Volume (cm³/mol) 29.14 30.09 30.28 29.28 30.67 28.79 29.63 29.56 29.30 29.63 Pre-IX Vickers Crack 1000- 1000- 1000- 500- 1000- 500- 1000- 1000- 1000- 1000- Initiation Load (gf) 2000 2000 2000 1000 2000 1000 2000 2000 2000 2000 Anneal Pt. (° C.) 610 606 630 624 605 623 605 614 613 624 Strain Pt. (° C.) 561 547 572 571 547 571 549 559 559 569 Temperature at Visc = 1206 1232 1246 1212 1237 1217 1227 1214 1211 1234 35 kP (° C.) Temperature Zircon >1250 Breakdown (° C.) Liquidus Viscosity (poise) 3.33E+09 9.74E+08 3.36E+08 1.34E+08 2.20E+10 Sample mol % 61 62 63 64 65 SiO₂ 58 58.8 58.8 60 60 B₂O₃ 3.75 4 4 4 4 Al₂O₃ 16.5 16.3 16.3 15.75 15.75 P₂O₅ 3.75 4 4 4 4 Na₂O 18 16.4 16.9 15.75 16.25 K₂O 0 0.5 0 0.5 0 SnO₂ 0 0 0 0 0 AlPO₄ equivalent BPO₄ equivalent M₂O₃ 20.25 20.3 20.3 19.75 19.75 P₂O₅ + R₂O 21.75 20.9 20.9 20.25 20.25 (P₂O₅ + R₂O)/M₂O₃ 1.07 1.03 1.03 1.03 1.03 (P₂O₅ + R₂O)/Al₂O₃ 1.32 1.28 1.28 1.29 1.29 Molar Volume (cm³/mol) 29.63 29.67 29.61 29.64 29.58 Pre-IX Vickers Crack 500- 1000- 1000- 1000- 1000- Initiation Load (gf) 1000 2000 2000 2000 2000 Anneal Pt. (° C.) 644 619 619 617 618 Strain Pt. (° C.) 585 565 565 563 563 Temperature at Visc = 1258 1229 1223 1235 1230 35 kP (° C.) Temperature Zircon Breakdown (° C.) Liquidus Viscosity (poise) 5.29E+09

TABLE 2 Compressive stress, crack initiation load, and abraded ring-on-ring failure loads for phosphate containing glasses ion exchanged at 410° C. Sample 1 2 3 4 5 6 7 8 9 10 410° C. 8 hr ion-exchange on annealed 0.7 mm thick samples Compressive Stress (MPa) 645 686 698 665 642 697 732 600 638 692 Depth of Layer (microns) 60 62 79 49 45 62 67 52 56 78 Vickers Crack Initiation Load (kgf) >30 >30 >30 >30 >30 >30 >30 >30 >30 >30 Abraded ring-on-ring load at failure >80 >80 >90 >70 >70 >100 >110 >60 >70 >120 (kgf) 410° C. 2 hr ion-exchange on annealed 0.7 mm thick samples Compressive Stress (MPa) 711 Depth of Layer (microns) 35 Vickers Crack Initiation Load (kgf) >30 Sample 11 12 13 14 15 16 17 18 19 20 410° C. 8 hr ion-exchange on annealed 0.7 mm thick samples Compressive Stress (MPa) 735 740 724 822 618 643 757 794 811 831 Depth of Layer (microns) 84 79 80 75 96 82 67 94 100 103 Vickers Crack Initiation Load (kgf) >30 >30 >30 >30 >30 >30 >30 >20 >20 15-20 Abraded ring-on-ring load at failure >140 >130 >130 >150 >130 >110 >110 >180 >190 >210 (kgf) 410° C. 2 hr ion-exchange on annealed 0.7 mm thick samples Compressive Stress (MPa) 774 817 836 838 871 Depth of Layer (microns) 39 42 45 50 53 Vickers Crack Initiation Load (kgf) >30 >30 25-30 >20 >20 Sample 21 22 23 24 25 26 27 28 29 30 410° C. 8 hr ion-exchange on annealed 0.7 mm thick samples Compressive Stress (MPa) 833 863 818 675 708 792 848 807 821 862 Depth of Layer (microns) 66 68 72 76 75 84 91 71 78 79 Vickers Crack Initiation Load (kgf) >30 >30 >30 >30 >25 >25 <20 20-25 20-25 20-25 Abraded ring-on-ring load at failure >130 >140 >140 >110 >110 >160 >190 >130 >150 >170 (kgf) 410° C. 2 hr ion-exchange on annealed 0.7 mm thick samples Compressive Stress (MPa) 872 897 880 Depth of Layer (microns) 33 34 38 Vickers Crack Initiation Load (kgf) >30 >30 >30 Sample 31 32 33 34 35 36 37 38 39 40 410° C. 8 hr ion-exchange on annealed 0.7 mm thick samples Compressive Stress (MPa) 802 838 657 793 763 763 853 981 740 680 Depth of Layer (microns) 81 81 69 71 82 78 68 59 66 64 Vickers Crack Initiation Load (kgf) 20-25 20-25 15-20 20-25 15-20 15-20 >25 >30 >30 >20 Abraded ring-on-ring load at failure >150 >160 >90 >130 >140 >130 >140 >160 >100 >120 (kgf) 410° C. 2 hr ion-exchanqe on annealed 0.7 mm thick samples Compressive Stress (MPa) Depth of Layer (microns) Vickers Crack Initiation Load (kgf) Sample 41 42 43 44 45 46 47 48 49 50 410° C. 8 hr ion-exchange on annealed 0.7 mm thick samples Compressive Stress (MPa) 787 882 740 857 728 672 765 892 951 809 Depth of Layer (microns) 77 59 63 66 56 69 66 74 59 57 Vickers Crack Initiation Load (kgf) >20 >20 >20 >20 >30 >30 20-25 >20 >20 >20 Abraded ring-on-ring load at failure >140 >130 >100 >140 >80 >90 >110 >170 >150 >100 (kgf) 410° C. 2 hr ion-exchange on annealed 0.7 mm thick samples Compressive Stress (MPa) 822 735 877 Depth of Layer (microns) 28 35 33 Vickers Crack Initiation Load (kgf) >30 >30 20-25 Sample 51 52 53 54 55 56 57 58 59 60 410° C. 8 hr ion-exchanqe on annealed 0.7 mm thick samples Compressive Stress (MPa) 856 709 690 784 624 852 748 774 793 785 Depth of Layer (microns) 52 54 78 78 64 58 66 63 61 63 Vickers Crack Initiation Load (kgf) >30 >20 >30 10-15 >20 10-15 >30 >30 >30 >30 Abraded ring-on-ring load at failure >100 >80 >120 >140 >80 >120 >110 >110 >110 >110 (kgf) 410° C. 2 hr ion-exchange on annealed 0.7 mm thick samples Compressive Stress (MPa) 948 Depth of Layer (microns) 27 Vickers Crack Initiation Load (kgf) >30 Sample 61 62 63 64 65 410° C. 8 hr ion-exchange on annealed 0.7 mm thick samples Compressive Stress (MPa) 863 796 805 796 787 Depth of Layer (microns) 64 66 65 65 64 Vickers Crack Initiation Load (kgf) >20 >20 >20 >20 >20 Abraded ring-on-ring load at failure >130 >120 >120 >120 >110 (kgf) 410° C. 2 hr ion-exchange on annealed 0.7 mm thick samples Compressive Stress (MPa) Depth of Layer (microns) Vickers Crack Initiation Load (kgf)

TABLE 3 Compressive stress, crack initiation load, and abraded ring-on-ring failure loads for phosphate containing glasses ion exchanged at 450° C. Sample 1 2 3 4 5 6 7 8 9 10 450° C. 30 min ion-exchange on annealed 0.7 mm thick samples Compressive Stress (MPa) Depth of Layer (microns) Vickers Crack Initiation Load (kgf) 450° C. 1 hr ion-exchange on annealed 0.7 mm thick samples Compressive Stress (MPa) Depth of Layer (microns) Vickers Crack Initiation Load (kgf) Sample 11 12 13 14 15 16 17 18 19 20 450° C. 30 min ion-exchange on annealed 0.7 mm thick samples Compressive Stress (MPa) 794 841 843 882 Depth of Layer (microns) 41 39 40 43 Vickers Crack Initiation Load (kgf) >30 25-30 20-25 15-20 450° C. 1 hr ion-exchange on annealed 0.7 mm thick samples Compressive Stress (MPa) 803 767 846 848 878 Depth of Layer (microns) 54 36 54 59 61 Vickers Crack Initiation Load (kgf) >30 >30 >20 20-25 >15 Sample 21 22 23 24 25 26 27 28 29 30 450° C. 30 min ion-exchange on annealed 0.7 mm thick samples Compressive Stress (MPa) 846 861 916 Depth of Layer (microns) 30 29 32 Vickers Crack Initiation Load (kgf) 20-25 20-25 20-25 450° C. 1 hr ion-exchange on annealed 0.7 mm thick samples Compressive Stress (MPa) 854 882 704 746 832 875 844 854 897 Depth of Layer (microns) 36 37 40 43 44 47 37 40 42 Vickers Crack Initiation Load (kgf) >30 >30 >30 >30 >30 <20 20-25 20-25 20-25 Sample 31 32 33 34 35 36 37 38 39 40 450° C. 30 min ion-exchange on annealed 0.7 mm thick samples Compressive Stress (MPa) 836 856 Depth of Layer (microns) 32 32 Vickers Crack Initiation Load (kgf) 20-25 20-25 450° C. 1 hr ion-exchange on annealed 0.7 mm thick samples Compressive Stress (MPa) 831 852 680 824 810 760 870 1032 Depth of Layer (microns) 42 43 40 42 46 46 39 32 Vickers Crack Initiation Load (kgf) 20-25 20-25 15-20 20-25 15-20 15-20 >30 >30 Sample 41 42 43 44 45 46 47 48 49 50 450° C. 30 min ion-exchange on annealed 0.7 mm thick samples Compressive Stress (MPa) Depth of Layer (microns) Vickers Crack Initiation Load (kgf) 450° C. 1 hr ion-exchange on annealed 0.7 mm thick samples Compressive Stress (MPa) 726 678 787 Depth of Layer (microns) 34 42 41 Vickers Crack Initiation Load (kgf) >30 >30 20-25 Sample 51 52 53 54 55 56 57 58 59 60 450° C. 30 min ion-exchange on annealed 0.7 mm thick samples Compressive Stress (MPa) Depth of Layer (microns) Vickers Crack Initiation Load (kgf) 450° C. 1 hr ion-exchange on annealed 0.7 mm thick samples Compressive Stress (MPa) 841 Depth of Layer (microns) 31 Vickers Crack Initiation Load (kgf) >30 Sample 61 62 63 64 65 450° C. 30 min ion-exchange on annealed 0.7 mm thick samples Compressive Stress (MPa) Depth of Layer (microns) Vickers Crack Initiation Load (kgf) 450° C. 1 hr ion-exchange on annealed 0.7 mm thick samples Compressive Stress (MPa) Depth of Layer (microns) Vickers Crack Initiation Load (kgf)

In another aspect, the phosphate-containing glasses described herein have an anneal point (i.e., the temperature at which the viscosity of the glass is 10^(12.2) Pascal seconds (Pa·s) (10^(13.2) poise (P)) of at least about 600° C., in other aspects, at least about 625° C., and in still other aspects, at least about 645° C., which is greater than those of high strength alkali aluminosilicate glasses and alkali aluminoborosilicate glasses. Anneal points for various compositions are listed in Table 1. The higher anneal point of the presently described glasses also reduces stress relaxation of the glass during ion exchange and enables ion exchange at higher temperatures. The higher anneal points also allows ion exchange of these glasses to be carried out at higher temperatures.

In those embodiments where the glass has a 35 kp temperature (i.e., the temperature at which the glass has a viscosity of 3.5 kPa·s (35 kilopoise (kP)) of less than 1300° C., the glasses described herein may be formed glass by down-draw methods that are known in the art, such as, for example, fusion-drawing and slot-drawing. Alternatively, the phosphate-containing glasses described herein can be formed by other methods known in the art such as, but not limited to, crucible melting, rolling, float methods, or the like. In addition to enabling glass formation by down-draw processes, the higher anneal points allows ion exchange of these glasses to be carried out at higher temperatures.

In some embodiments, the phosphate-containing glasses described herein are down-drawable by processes known in the art, such as slot-drawing, fusion drawing, re-drawing, and the like, and has a liquidus viscosity of at least 130 kilopoise

In some embodiments, the phosphate-containing glasses described herein have a temperature T_(35kp) at which the glass has a viscosity of 35 kpoise, wherein the temperature T_(breakdown) at which zircon breaks down to form ZrO₂ and SiO₂ is greater than T^(35kp).

FIG. 3 is a plot of compressive stress and depth of layer as functions of AlPO₄ concentration for 0.7 mm thick phosphate-containing glasses (samples 13 and 18-20 in Tables 1-3) phosphate-containing glasses described herein after ion exchange in a molten KNO₃ salt bath for 1 hour at 450° C. As seen in FIG. 3, these glasses are capable of ion exchange under the above conditions to a depth of layer of at least 50 μm and a compressive stress of at least 800 MPa. FIG. 4 is a plot of compressive stress and depth of layer as functions of AlPO₄ concentration for 0.7 mm thick phosphate-containing glasses described herein (samples 13 and 18-20 in Tables 1-3) after ion exchange in a molten KNO₃ salt bath for 30 minutes at 450° C. Compressive stresses and depths of layer obtained by ion exchange in a molten KNO₃ salt bath at 450° C. for 30 minutes and 1 hour of the phosphate-containing glasses described herein, as well as Vickers indentation/crack initiation thresholds and abraded ring-on-ring failure loads for these ion exchange glasses, are listed in Table 3.

In one aspect, the phosphate-containing glasses described herein, when chemically strengthened by ion exchange, exhibit a Vickers initiation cracking threshold of at least about 10 kgf (kilogram force), in some embodiments, at least about 20 kgf, in some embodiments and, in other embodiments, at least about 30 kgf. Vickers initiation cracking thresholds measured for 0.7 mm thick phosphate-containing glasses (samples 13 and 18-20 in Table 1) that were ion exchanged in a molten KNO₃ salt bath at 450° C. for 30 minutes are plotted as a function of AlPO₄ concentration in FIG. 5. Each of the samples for which data are plotted in FIG. 5 do not contain boron and have (P₂O₅+R₂O)/M₂O₃ and (P₂O₅+R₂O)/Al₂O₃ ratios that are equal to 1. In another aspect, the phosphate-containing glasses described herein, when chemically strengthened by ion exchange, fail at loads of greater than about 80 kgf when subjected to an abraded ring-on-ring load.

The glasses described herein may be used in applications such has, but not limited to: touch screens; protective cover glass for electronic devices such as a hand held communication or entertainment devices, information-related terminals, touch sensor devices, or the like; windshields; appliance enclosures; or architectural elements such as windows, panels, or the like.

While typical embodiments have been set forth for the purpose of illustration, the foregoing description should not be deemed to be a limitation on the scope of the disclosure or appended claims. Accordingly, various modifications, adaptations, and alternatives may occur to one skilled in the art without departing from the spirit and scope of the present disclosure or appended claims. 

The invention claimed is:
 1. A glass comprising: 40 to 64 mol % SiO₂, 18.5 to 28 mol % Al₂O₃, 1 to 14 mol % P₂O₅, K₂O, and at least one alkali metal oxide (R₂O), wherein R₂O is selected from the group consisting of Na₂O and K₂O, wherein 0.75≤[(P₂O₅ (mol %)+R₂O (mol %))/M₂O₃ (mol %)]≤1.0, where M₂O₃=Al₂O₃, and wherein the glass is lithium-free.
 2. The glass of claim 1, wherein the glass is ion exchanged, and wherein the glass has a Vickers crack initiation threshold of at least about 20 kgf.
 3. The glass of claim 1, wherein the glass is ion exchanged to a depth of layer of at least about 40 μm from a surface of the glass.
 4. The glass of claim 3, wherein the glass is ion exchanged to a depth of layer extending at least about 60 μm from a surface of the glass.
 5. The glass of claim 1, wherein the glass is ion exchanged, and wherein the glass fails at a load of greater than about 80 kgf when subjected to abraded ring-on-ring loading.
 6. The glass of claim 1, wherein the glass has an anneal point of at least about 600° C.
 7. The glass of claim 1, wherein the glass comprises: about 12 to about 16 mol % R₂O.
 8. The glass of claim 1, wherein the glass comprises: about 2 to about 12% P₂O₅.
 9. The glass of claim 1, wherein aluminum is present in the glass in the form of tetrahedral aluminum oxide units and phosphorus is present in the glass in the form of tetrahedral phosphorus oxide units.
 10. The glass of claim 9, wherein the tetrahedral aluminum oxide and tetrahedral phosphorus oxide units replace tetrahedral silica units in the glass.
 11. The glass of claim 1, wherein boron is present in the glass in the form of tetrahedral boron oxide units and phosphorus is present in the form of tetrahedral phosphorus oxide units.
 12. The glass of claim 11, wherein the tetrahedral boron oxide and tetrahedral phosphorus oxide units replace tetrahedral silica units in the glass.
 13. The glass of claim 1, wherein the glass is substantially free of non-bridging oxygen atoms.
 14. The glass of claim 1, wherein [(P₂O₅ (mol %)+R₂O (mol %))/M₂O₃ (mol %)]=1.
 15. The glass of claim 1, wherein the molar volume of the glass is at least about 29 cm³/mol.
 16. The glass of claim 1, wherein the glass has a depth of layer extending to at least about 30 μm from a surface of the glass when ion exchanged in an ion exchange bath comprising KNO₃ at 410° C. for 2 hours.
 17. The glass of claim 1, wherein the glass is ion exchanged and has a Vickers crack initiation threshold of at least about 10 kgf.
 18. The glass of claim 1, comprising about 12 to about 18 mol % R₂O.
 19. The glass of claim 1, further comprising B₂O₃.
 20. An electronic device comprising a cover glass, wherein the cover glass comprises the glass of claim
 1. 